182 Moretti, Poisson, and Marsura
5-(6-(Bromomethyl)-pyridin-2-yl)-3-methyl-1,2,4-
triazine 10 [8]. N-Bromosuccinimide (0.870 g,
4.89 mmol) and AIBN (0.081 g, 0.49 mmol) were
added to a solution of 6 (1 g, 5.37 mmol) into CCl4
(50 mL) under argon. The reaction mixture was
stirred 75 min. under reflux and irradiation with a
(100-W) tungsten lamp. After reaction, the mixture
was filtered, and the solid phase was washed three
times with CCl4. After evaporation of the solvent,
the residue was chromatographed on a silica gel 60
Merck (0.04–0.063 mm) column; with CH2Cl2/Et2O :
9/1 as the eluent. The pure product 10 was obtained
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1
as a yellow solid: 0.436 g (31%). H NMR (CDCl3;
25°C) δ: 10.05 (s, 1H), 8.39 (d, J = 7.8 Hz, 1H), 7.84
(t, J = 7.8Hz), 7.57 (d, J = 7.8Hz,1H), 4.57 (s, 2H),
2.88 (s, 3H); 13C NMR (CDCl3; 25°C) δ 167.2, 157.8,
153.6, 152.2, 144.9, 138.8, 122.2, 33.6, 24.3; MS (CI):
m/z 265 [M]+, 185 [M – Br]+, 116 [M – Br – N2]+;
Anal. Calcd. for C10H9BrN4: C, 45.30; H, 3.41; N,
21.10. Found: C, 45.05; H, 3.72; N, 20.98.
3-(Chloromethyl)-5-(6-methylpyridin-2-yl)-1,2,4-
triazine 11 [8]. A mixture of 6 (0.020 g, 0.11 mmol),
TCDGU (0.046 g, 0.11 mmol) and AIBN (0.001 g,
0.005 mmol) was stirred 24 h at 78°C into degased
toluene (2 mL) under argon and irradiation with a
(100-W) tungsten lamp. The resulting suspension
was filtered, and the solid phase was washed with
toluene (3 × 5 mL). After evaporation of the solvent,
the residue was chromatographed on a silicagel 60
Merck (0.04–0.063-mm) column; with CH2Cl2 as
the eluent. The pure product 11 was obtained as a
yellow solid: 0.025 g, (10%). 1H NMR (CDCl3; 25°C)
δ: 10.16 (s, 1H), 8.33 (d, J = 7.8 Hz, 1H), 7.73 (t, J
= 7.8, 1H), 7.28 (d, J = 7.8 Hz, 1H), 4.90 (s, 2H),
2.60 (s, 3H); 13C NMR (CDCl3; 25°C) δ 165.3, 159.6,
155.2, 151.1, 146.2, 137.9, 126.9, 120.7, 45.5, 24.9;
MS (EI): m/z 221 [M]+; Anal. Calcd. for C10H9ClN4:
C, 54.42; H, 4.11; N, 25.30. Found: C, 54.31; H, 4.05;
N 25.31.
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ACKNOWLEDGMENTS
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Financial supports from the CNRS and the French
“Ministe`re de l’Enseignement Supe´rieur et de la
Recherche,” Universite´ Paris 11, and Ecole Centrale
Paris are gratefully acknowledged. Mrs. S. Adache
for elemental analyses, Mr. F. Dupire for the ESI
mass spectra registration, Dr. Diem Ngan Tran for
some results in synthesis, Drs. V. Bulach, Nouha
El Hassan and S. Dahaouifor their help in X-ray
data collection, and the joint service of NMR are
also acknowledged. The authors warmly thank Pr. C.
Thirion for helpful discussions around experimental
design and Dr. J.-P. Joly for the insightful discussion
on the manuscript.
Heteroatom Chemistry DOI 10.1002/hc